KR20180059472A - High purity carboxylic acid esters and methods for their preparation - Google Patents
High purity carboxylic acid esters and methods for their preparation Download PDFInfo
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- KR20180059472A KR20180059472A KR1020187010671A KR20187010671A KR20180059472A KR 20180059472 A KR20180059472 A KR 20180059472A KR 1020187010671 A KR1020187010671 A KR 1020187010671A KR 20187010671 A KR20187010671 A KR 20187010671A KR 20180059472 A KR20180059472 A KR 20180059472A
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- exchange resin
- carboxylic acid
- acid ester
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- 150000001733 carboxylic acid esters Chemical class 0.000 title claims abstract description 64
- 238000000034 method Methods 0.000 title claims description 37
- 239000012535 impurity Substances 0.000 claims abstract description 70
- 239000003957 anion exchange resin Substances 0.000 claims abstract description 57
- NWUYHJFMYQTDRP-UHFFFAOYSA-N 1,2-bis(ethenyl)benzene;1-ethenyl-2-ethylbenzene;styrene Chemical compound C=CC1=CC=CC=C1.CCC1=CC=CC=C1C=C.C=CC1=CC=CC=C1C=C NWUYHJFMYQTDRP-UHFFFAOYSA-N 0.000 claims abstract description 49
- 239000003729 cation exchange resin Substances 0.000 claims abstract description 38
- 229910052751 metal Inorganic materials 0.000 claims abstract description 32
- 239000002184 metal Substances 0.000 claims abstract description 32
- 125000000129 anionic group Chemical group 0.000 claims abstract description 26
- 229910052804 chromium Inorganic materials 0.000 claims abstract description 15
- 229910052742 iron Inorganic materials 0.000 claims abstract description 15
- 229910052700 potassium Inorganic materials 0.000 claims abstract description 14
- 229910052709 silver Inorganic materials 0.000 claims abstract description 14
- 229910052708 sodium Inorganic materials 0.000 claims abstract description 14
- 229910052718 tin Inorganic materials 0.000 claims abstract description 14
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 12
- 229910052802 copper Inorganic materials 0.000 claims abstract description 12
- 229910052749 magnesium Inorganic materials 0.000 claims abstract description 12
- 229910052725 zinc Inorganic materials 0.000 claims abstract description 12
- LZCLXQDLBQLTDK-UHFFFAOYSA-N ethyl 2-hydroxypropanoate Chemical compound CCOC(=O)C(C)O LZCLXQDLBQLTDK-UHFFFAOYSA-N 0.000 claims description 16
- XYVQFUJDGOBPQI-UHFFFAOYSA-N Methyl-2-hydoxyisobutyric acid Chemical compound COC(=O)C(C)(C)O XYVQFUJDGOBPQI-UHFFFAOYSA-N 0.000 claims description 8
- 229940116333 ethyl lactate Drugs 0.000 claims description 8
- 238000004519 manufacturing process Methods 0.000 claims description 6
- -1 methyl β-hydroxyisobutyrate Chemical compound 0.000 claims description 3
- LPEKGGXMPWTOCB-UHFFFAOYSA-N 8beta-(2,3-epoxy-2-methylbutyryloxy)-14-acetoxytithifolin Natural products COC(=O)C(C)O LPEKGGXMPWTOCB-UHFFFAOYSA-N 0.000 claims description 2
- ODQWQRRAPPTVAG-GZTJUZNOSA-N doxepin Chemical group C1OC2=CC=CC=C2C(=C/CCN(C)C)/C2=CC=CC=C21 ODQWQRRAPPTVAG-GZTJUZNOSA-N 0.000 claims description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 2
- 229940057867 methyl lactate Drugs 0.000 claims description 2
- ILVGAIQLOCKNQA-UHFFFAOYSA-N propyl 2-hydroxypropanoate Chemical compound CCCOC(=O)C(C)O ILVGAIQLOCKNQA-UHFFFAOYSA-N 0.000 claims description 2
- 239000003377 acid catalyst Substances 0.000 claims 1
- 239000002253 acid Substances 0.000 abstract description 7
- 229910000838 Al alloy Inorganic materials 0.000 abstract 1
- 150000002148 esters Chemical class 0.000 abstract 1
- 230000002378 acidificating effect Effects 0.000 description 17
- 239000011734 sodium Substances 0.000 description 10
- 125000000962 organic group Chemical group 0.000 description 8
- 150000001450 anions Chemical class 0.000 description 7
- 230000000052 comparative effect Effects 0.000 description 7
- 239000007788 liquid Substances 0.000 description 7
- 239000004065 semiconductor Substances 0.000 description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 7
- 239000003456 ion exchange resin Substances 0.000 description 6
- 229920003303 ion-exchange polymer Polymers 0.000 description 6
- 229940023913 cation exchange resins Drugs 0.000 description 5
- 238000006460 hydrolysis reaction Methods 0.000 description 4
- 239000011347 resin Substances 0.000 description 4
- 229920005989 resin Polymers 0.000 description 4
- 239000000758 substrate Substances 0.000 description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 239000000853 adhesive Substances 0.000 description 3
- 230000001070 adhesive effect Effects 0.000 description 3
- 229910052783 alkali metal Inorganic materials 0.000 description 3
- 150000001340 alkali metals Chemical class 0.000 description 3
- 238000004458 analytical method Methods 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 238000004140 cleaning Methods 0.000 description 3
- 239000012459 cleaning agent Substances 0.000 description 3
- 238000005530 etching Methods 0.000 description 3
- 239000012458 free base Substances 0.000 description 3
- 150000002739 metals Chemical class 0.000 description 3
- 229920002120 photoresistant polymer Polymers 0.000 description 3
- 238000000746 purification Methods 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- 238000003860 storage Methods 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- JGFBQFKZKSSODQ-UHFFFAOYSA-N Isothiocyanatocyclopropane Chemical compound S=C=NC1CC1 JGFBQFKZKSSODQ-UHFFFAOYSA-N 0.000 description 2
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 2
- 239000002585 base Substances 0.000 description 2
- PWLNAUNEAKQYLH-UHFFFAOYSA-N butyric acid octyl ester Natural products CCCCCCCCOC(=O)CCC PWLNAUNEAKQYLH-UHFFFAOYSA-N 0.000 description 2
- 229910052791 calcium Inorganic materials 0.000 description 2
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 238000000354 decomposition reaction Methods 0.000 description 2
- 238000002845 discoloration Methods 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 229910052737 gold Inorganic materials 0.000 description 2
- 230000007062 hydrolysis Effects 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 229910021645 metal ion Inorganic materials 0.000 description 2
- 239000007769 metal material Substances 0.000 description 2
- UUIQMZJEGPQKFD-UHFFFAOYSA-N n-butyric acid methyl ester Natural products CCCC(=O)OC UUIQMZJEGPQKFD-UHFFFAOYSA-N 0.000 description 2
- 239000003973 paint Substances 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- BKBZFJRHYSCZQA-UHFFFAOYSA-N 2-methoxy-2-methylpropanoic acid Chemical compound COC(C)(C)C(O)=O BKBZFJRHYSCZQA-UHFFFAOYSA-N 0.000 description 1
- 150000001342 alkaline earth metals Chemical class 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-O ammonium group Chemical group [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- 230000001174 ascending effect Effects 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000002091 cationic group Chemical group 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 238000001095 inductively coupled plasma mass spectrometry Methods 0.000 description 1
- 230000000977 initiatory effect Effects 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 238000002203 pretreatment Methods 0.000 description 1
- 238000005086 pumping Methods 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 125000000542 sulfonic acid group Chemical group 0.000 description 1
- 238000004448 titration Methods 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
- C07C67/48—Separation; Purification; Stabilisation; Use of additives
- C07C67/56—Separation; Purification; Stabilisation; Use of additives by solid-liquid treatment; by chemisorption
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J39/00—Cation exchange; Use of material as cation exchangers; Treatment of material for improving the cation exchange properties
- B01J39/04—Processes using organic exchangers
- B01J39/05—Processes using organic exchangers in the strongly acidic form
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J39/00—Cation exchange; Use of material as cation exchangers; Treatment of material for improving the cation exchange properties
- B01J39/08—Use of material as cation exchangers; Treatment of material for improving the cation exchange properties
- B01J39/16—Organic material
- B01J39/18—Macromolecular compounds
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J39/00—Cation exchange; Use of material as cation exchangers; Treatment of material for improving the cation exchange properties
- B01J39/26—Cation exchangers for chromatographic processes
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J41/00—Anion exchange; Use of material as anion exchangers; Treatment of material for improving the anion exchange properties
- B01J41/04—Processes using organic exchangers
- B01J41/07—Processes using organic exchangers in the weakly basic form
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J41/00—Anion exchange; Use of material as anion exchangers; Treatment of material for improving the anion exchange properties
- B01J41/08—Use of material as anion exchangers; Treatment of material for improving the anion exchange properties
- B01J41/12—Macromolecular compounds
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J41/00—Anion exchange; Use of material as anion exchangers; Treatment of material for improving the anion exchange properties
- B01J41/20—Anion exchangers for chromatographic processes
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J47/00—Ion-exchange processes in general; Apparatus therefor
- B01J47/02—Column or bed processes
- B01J47/026—Column or bed processes using columns or beds of different ion exchange materials in series
- B01J47/028—Column or bed processes using columns or beds of different ion exchange materials in series with alternately arranged cationic and anionic exchangers
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C69/00—Esters of carboxylic acids; Esters of carbonic or haloformic acids
- C07C69/66—Esters of carboxylic acids having esterified carboxylic groups bound to acyclic carbon atoms and having any of the groups OH, O—metal, —CHO, keto, ether, acyloxy, groups, groups, or in the acid moiety
- C07C69/67—Esters of carboxylic acids having esterified carboxylic groups bound to acyclic carbon atoms and having any of the groups OH, O—metal, —CHO, keto, ether, acyloxy, groups, groups, or in the acid moiety of saturated acids
- C07C69/675—Esters of carboxylic acids having esterified carboxylic groups bound to acyclic carbon atoms and having any of the groups OH, O—metal, —CHO, keto, ether, acyloxy, groups, groups, or in the acid moiety of saturated acids of saturated hydroxy-carboxylic acids
- C07C69/68—Lactic acid esters
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Analytical Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
본 발명에 의하면, 금속 불순물로서 Ag, Al, Au, Ca, Cr, Cu, Fe, K, Mg, Na, Sn 및 Zn의 각각의 함유율이 1ppb 미만이고, 음이온성 불순물의 함유율이 1ppm 미만인, 고순도 카복실산 에스터를 제공할 수 있다. 또, 본 발명에 의하면, 금속 불순물로서 Ag, Al, Au, Ca, Cr, Cu, Fe, K, Mg, Na, Sn 및 Zn과, 음이온성 불순물을 포함하는 미정제 카복실산 에스터를, 양이온 교환 수지(II)에 접촉시키는 공정과, 이어서 음이온 교환 수지(III)에 접촉시키는 공정을 포함하는, 고순도 카복실산 에스터의 제조 방법을 제공할 수 있다.According to the present invention, it is possible to obtain a high-purity aluminum alloy having a content ratio of each of Ag, Al, Au, Ca, Cr, Cu, Fe, K, Mg, Na, Sn and Zn of less than 1 ppb and an anionic impurity content of less than 1 ppm Carboxylic < / RTI > acid ester. According to the present invention, the crude carboxylic acid ester containing Ag, Al, Au, Ca, Cr, Cu, Fe, K, Mg, Na, Sn and Zn as the metal impurities and anionic impurities is mixed with the cation exchange resin (II) in the presence of an anion exchange resin (III), and subsequently contacting the anion exchange resin (III) with the anion exchange resin (III).
Description
본 발명은 금속 불순물 및 음이온성 불순물을 저감한 카복실산 에스터의 정제 방법에 관한 것이다. 본 발명의 카복실산 에스터는 합성 원료, 전자 부품의 세정제나 도료, 접착제 등의 용제 등의 폭넓은 용도에 유용하다. 또한, 집적 회로나 대규모 집적 회로의 제조에 있어서의 반도체 기판의 세정, 식각, 포토레지스트의 현상 등을 위한 처리제로서 사용된다. 특히, 반도체용의 용도에 있어서는, 반도체 기판이 오염되기 때문에 매우 고순도일 것이 요구되어, 가능한 한 불순물을 함유하지 않는 고순도의 카복실산 에스터가 필요하다고 여겨지고 있다.The present invention relates to a method for purifying a carboxylic acid ester in which metal impurities and anionic impurities are reduced. The carboxylic acid ester of the present invention is useful for a wide variety of applications such as a synthesis raw material, a cleaning agent for electronic components, a coating agent, and a solvent such as an adhesive. It is also used as a treating agent for cleaning, etching, developing photoresist, etc. of semiconductor substrates in the manufacture of integrated circuits and large-scale integrated circuits. Particularly, in applications for semiconductors, since the semiconductor substrate is contaminated, it is required to be extremely high in purity, and it is considered that a high-purity carboxylic acid ester containing no impurities is required as much as possible.
그렇지만, 종래 이용되고 있는 카복실산 에스터는 금속 불순물이나 음이온성 불순물의 농도가 높아, 반도체 용도에 있어서는 사용할 수 없는 등의 문제가 있었다.However, conventionally used carboxylic acid esters have high concentrations of metal impurities and anionic impurities, and thus have problems such as being unusable in semiconductor applications.
예를 들면 특허문헌 1에는, 카복실산 에스터의 저장 안정성 및 금속 재료에 대한 부식성을 개선하기 위한 기술로서, 카복실산 에스터 중의 함수량을 제한하는 방법이 기재되어 있다. 그리고, 당해 문헌에는, 함수량을 제한하는 것에 의해 카복실산 에스터의 가수분해를 억제하여, 금속 재료의 부식 등의 원인이 되는 산 성분(카복실산 에스터의 가수분해물)의 증가를 억제하는 방법이 기재되어 있지만, 금속 불순물의 저감에 대해서는 아무것도 언급되어 있지 않다.For example, Patent Document 1 discloses a method for limiting the water content in a carboxylic acid ester as a technique for improving the storage stability of a carboxylic acid ester and the corrosiveness to a metal material. In this document, there is described a method for suppressing hydrolysis of a carboxylic acid ester by restricting the water content and suppressing an increase in an acid component (hydrolyzate of a carboxylic acid ester) which causes corrosion of the metal material. However, Nothing is mentioned about reduction of metallic impurities.
특허문헌 2에는, 카복실산 에스터 중의 산 성분을 중화 등에 의해 저감하여, 저장 중의 분해, 변색과 같은 저장 안정성을 개선하는 방법이 기재되어 있다. 이 방법에 있어서도 카복실산 에스터 자체의 분해, 변색을 억제하고 있는 것에 불과하고, 당해 문헌에는 금속 불순물의 저감에 대해서는 아무것도 언급되어 있지 않다.Patent Document 2 discloses a method for reducing the acid component in a carboxylic acid ester by neutralization or the like to improve storage stability such as decomposition and discoloration during storage. This method is merely suppressing the decomposition and discoloration of the carboxylic acid ester itself, and nothing about the reduction of metal impurities is mentioned in this document.
특허문헌 3에는, 알칼리 금속 및 알칼리 토류 금속 양이온의 함유율을 저감시키기 위해서, 실질적으로 무수의 유기 액체를 1종 또는 복수종의 양이온 교환 수지와 접촉시키는 방법이 기재되어 있다. 당해 문헌에는, 저감하는 금속 양이온종이 알칼리 금속 및 알칼리 토류 금속으로 한정되고, 음이온성 불순물의 저감에 관한 기재는 없기 때문에, 카복실산 에스터의 정제 방법으로서는 불충분하다.Patent Document 3 describes a method in which a substantially anhydrous organic liquid is contacted with one or more cation exchange resins in order to reduce the contents of alkali metal and alkaline earth metal cations. In this document, the metal cationic species to be reduced are limited to alkali metals and alkaline earth metals, and since there is no description about reduction of anionic impurities, it is insufficient as a method for purifying a carboxylic acid ester.
특허문헌 4, 5에는, 이온 교환 수지를 이용하여 비수 액상물에 포함되는 금속 이온 등의 제거를 행할 때에, 양이온 교환 수지 단독, 또는 양이온 교환 수지와 음이온 교환 수지의 혼합 이온 교환 수지에 비수 액상물을 접촉시켜, 비수 액상물 중의 금속 불순물을 극히 낮은 농도로까지 저감시키고, 수지 자신으로부터의 용출물도 제거하여 극히 고순도인 정제를 할 수 있는 방법이 기재되어 있다. 그러나, 정제 후의 Na 농도는 50ppb 이하로 반도체용 용도로서 필요한 금속 불순물 농도인 1ppb 이하를 만족시키고 있지 않아, 카복실산 에스터의 정제 방법으로서는 불충분하다.Patent Documents 4 and 5 disclose a method in which when a metal ion or the like contained in a non-aqueous liquid is removed using an ion exchange resin, a cation exchange resin alone or a mixed ion exchange resin of a cation exchange resin and an anion exchange resin is added to a non- To reduce the metal impurities in the non-aqueous liquid to an extremely low concentration, and to remove the eluted material from the resin itself, thereby making it possible to carry out purification with extremely high purity. However, the Na concentration after purification is not more than 50 ppb, which is not enough to satisfy the metal impurity concentration of 1 ppb or less, which is necessary for semiconductor applications, and is insufficient as a method for purifying a carboxylic acid ester.
특허문헌 6에는, 강염기성 음이온 교환 수지의 대(對)이온으로서 OH 또는 약산을 가지는 이온 교환 수지를 이용하는 것에 의해, 유기 용매 중의 금속 이온을 제거할 수 있는 방법이 기재되어 있다. 그러나, 제거할 수 있는 금속 불순물로서 Fe, Pd가 기재되어 있을 뿐이고, 다른 알칼리 금속 등의 불순물 제거에 관해서는 언급이 없어, 카복실산 에스터의 정제 방법으로서는 불충분하다. 이와 같이, 카복실산 에스터를 고도로 정제하는 방법은 아직 알려져 있지 않다.Patent Document 6 discloses a method capable of removing metal ions in an organic solvent by using an ion exchange resin having OH or weak acid as a counter ion of a strongly basic anion exchange resin. However, only Fe and Pd are described as metal impurities that can be removed, and there is no mention of the removal of impurities such as other alkali metals, which is insufficient as a method for purifying a carboxylic acid ester. Thus, a method for highly purifying a carboxylic acid ester is not yet known.
본 발명의 목적은 금속 불순물 및 음이온성 불순물이 매우 저감된 고순도의 카복실산 에스터를 제공하는 것이다.It is an object of the present invention to provide a high-purity carboxylic acid ester in which metal impurities and anionic impurities are greatly reduced.
본 발명자들은 이들 과제를 해결하기 위하여, 카복실산 에스터의 정제 방법에 대해 예의 연구를 행한 결과, 카복실산 에스터로부터 금속 불순물 및 음이온성 불순물을 제거할 때에 이온 교환 수지를 이용하고, 나아가 양이온 교환 수지 및 음이온 교환 수지에 통액하는 순서를 규정하는 것에 의해, 카복실산 에스터를 고도로 정제할 수 있음을 발견하여, 본 발명을 완성시키기에 이르렀다.In order to solve these problems, the inventors of the present invention have conducted intensive studies on a method for purifying a carboxylic acid ester. As a result, it has been found that an ion exchange resin is used in removing a metal impurity and an anionic impurity from a carboxylic acid ester, It has been found that the carboxylic acid ester can be highly purified by regulating the flow of the liquid through the resin, thereby completing the present invention.
즉, 본 발명은 이하와 같다.That is, the present invention is as follows.
<1> 금속 불순물로서 Ag, Al, Au, Ca, Cr, Cu, Fe, K, Mg, Na, Sn 및 Zn의 각각의 함유율이 1ppb 미만이고, 음이온성 불순물의 함유율이 1ppm 미만인, 고순도 카복실산 에스터이다.A high-purity carboxylic acid ester having a content of each of Ag, Al, Au, Ca, Cr, Cu, Fe, K, Mg, Na, Sn and Zn as a metal impurity of less than 1 ppb and an anionic impurity content of less than 1 ppm to be.
<2> 금속 불순물로서 적어도 Ag, Al, Au, Ca, Cr, Cu, Fe, K, Mg, Na, Sn 및 Zn과, 음이온성 불순물을 포함하는 미정제 카복실산 에스터를, 양이온 교환 수지(II)에 접촉시키는 공정과, 이어서 음이온 교환 수지(III)에 접촉시키는 공정을 포함하는 것을 특징으로 하는, 고순도 카복실산 에스터의 제조 방법이다.(2) A process for producing a cation exchange resin (II), which comprises reacting a crude carboxylic acid ester containing at least Ag, Al, Au, Ca, Cr, Cu, Fe, K, Mg, Na, Sn and Zn and an anionic impurity as metal impurities, (III), and a step of bringing the anion exchange resin (III) into contact with the anion exchange resin (III).
<3> 상기 양이온 교환 수지(II)에 접촉시키기 전에, 음이온 교환 수지(I)에 접촉시키는 공정을 포함하는, 상기 <2>에 기재된 고순도 카복실산 에스터의 제조 방법이다.<3> The method for producing a high purity carboxylic acid ester according to <2>, which comprises a step of bringing the anion exchange resin (I) into contact with the cation exchange resin (II) before being contacted.
<4> 상기 카복실산 에스터가 락트산 메틸, 락트산 에틸, 락트산 프로필, α-하이드록시아이소뷰티르산 메틸, α-하이드록시아이소뷰티르산 에틸, α-하이드록시아이소뷰티르산 프로필, α-하이드록시아이소뷰티르산 뷰틸, β-하이드록시아이소뷰티르산 메틸, β-하이드록시아이소뷰티르산 에틸, β-하이드록시아이소뷰티르산 프로필 및 β-하이드록시아이소뷰티르산 뷰틸로 이루어지는 군으로부터 선택되는 적어도 1종인, 상기 <2> 또는 <3>에 기재된 고순도 카복실산 에스터의 제조 방법이다.<4> The composition according to <4>, wherein the carboxylic acid ester is selected from the group consisting of methyl lactate, ethyl lactate, propyl lactate, methyl α- Which is at least one member selected from the group consisting of butyl,? -Hydroxyisobutyrate,? -Hydroxyisobutyrate,? -Hydroxyisobutyrate, and? -Hydroxyisobutyrate, Or < 3 >.
<5> 얻어진 고순도 카복실산 에스터에 있어서, 상기 금속 불순물의 함유율이 Ag, Al, Au, Ca, Cr, Cu, Fe, K, Mg, Na, Sn 및 Zn에 대해 각각 1ppb 미만이고, 상기 음이온성 불순물의 함유율이 1ppm 미만인, 상기 <2>∼<4> 중 어느 하나에 기재된 고순도 카복실산 에스터의 제조 방법이다.<5> The high purity carboxylic acid ester according to any one of <1> to <5>, wherein the metal impurity content is less than 1 ppb for each of Ag, Al, Au, Ca, Cr, Cu, Fe, K, Mg, Na, Sn and Zn, The process for producing a high purity carboxylic acid ester according to any one of < 2 > to < 4 >
<6> 상기 미정제 카복실산 에스터에 있어서, 상기 금속 불순물의 함유율이 Ag, Al, Au, Ca, Cr, Cu, Fe, K, Mg, Na, Sn 및 Zn에 대해 각각 8ppb 이상이고, 상기 음이온 불순물의 함유량이 20ppm 이상인, 상기 <2>∼<5> 중 어느 하나에 기재된 고순도 카복실산 에스터의 제조 방법이다.<6> The crude carboxylic acid ester according to any one of <1> to <6>, wherein the content of the metal impurity is 8 ppb or more for each of Ag, Al, Au, Ca, Cr, Cu, Fe, K, Mg, Na, Sn and Zn, Is a process for producing a high purity carboxylic acid ester according to any one of < 2 > to < 5 >
본 발명의 방법에 의해 얻어지는 고순도 카복실산 에스터는 금속 불순물 및 음이온성 불순물이 고도로 저감되어 있어, 카복실산 에스터가 이용되는 많은 용도, 특히 전자 공업용의 용도에 적합하게 사용 가능하다. 구체적으로는, 합성 원료, 전자 부품의 세정제나 도료, 접착제 등의 용제 등의 폭넓은 용도로서, 또한 집적 회로나 대규모 집적 회로의 제조에 있어서의 반도체 기판의 세정, 식각, 포토레지스트의 현상 등을 위한 처리제로서 사용된다. 따라서, 본 발명의 공업적 의의는 크다.The high purity carboxylic acid ester obtained by the method of the present invention is highly reduced in metal impurities and anionic impurities, and can be suitably used for many uses in which a carboxylic acid ester is used, in particular, for use in the electronic industry. More specifically, the present invention relates to a method for cleaning, etching, and developing a photoresist of a semiconductor substrate in a wide range of applications such as a synthesis raw material, a cleaning agent for electronic components, a solvent such as a paint or an adhesive, ≪ / RTI > Therefore, the industrial significance of the present invention is large.
도 1은 실시예 1 및 2에 있어서, 카복실산 에스터를 약염기성 음이온 교환 수지(I), 강산성 양이온 교환 수지(II) 및 약염기성 음이온 교환 수지(III)의 순으로 통액하여 고순도 카복실산 에스터를 얻는 과정을 나타내는 개략도이다.1 is a view showing a process of obtaining a high purity carboxylic acid ester by passing a carboxylic acid ester through a weakly basic anion exchange resin (I), a strongly acidic cation exchange resin (II) and a weakly basic anion exchange resin (III) in the order of Examples 1 and 2, Fig.
이하, 본 발명을 구체적으로 설명한다. 본 발명은 금속 불순물의 함유율이 각 금속종에 대해 1ppb 미만이고, 음이온성 불순물의 함유율이 1ppm 미만인 고순도 카복실산 에스터, 및 그의 제조 방법이다.Hereinafter, the present invention will be described in detail. The present invention is a high-purity carboxylic acid ester having a metal impurity content of less than 1 ppb for each metal species and a content of an anionic impurity of less than 1 ppm, and a process for producing the same.
본 발명의 고순도 카복실산 에스터는, 금속 불순물 및 음이온성 불순물을 포함하는 미정제 카복실산 에스터를 양이온 교환 수지 및 음이온 교환 수지에 접촉시키는 것에 의해, 양이온 교환 수지 및 음이온 교환 수지의 양방에 의해 금속 불순물을 제거하고, 음이온 교환 수지에 의해 음이온성 불순물을 제거하는 것에 의해 제조된다. 본 발명에 있어서의 음이온성 불순물로서는, 미정제 카복실산 에스터 중에 포함되는, 당해 카복실산 에스터의 가수분해 반응에 의해 생기는 카복실산을 들 수 있다.The high purity carboxylic acid ester of the present invention can be obtained by removing metal impurities by both cation exchange resin and anion exchange resin by bringing the crude carboxylic acid ester containing metal impurities and anionic impurities into contact with the cation exchange resin and the anion exchange resin And removing the anionic impurities by an anion exchange resin. Examples of the anionic impurities in the present invention include a carboxylic acid contained in the crude carboxylic acid ester and generated by the hydrolysis reaction of the carboxylic acid ester.
본 발명에 있어서의 미정제 카복실산 에스터는 금속 불순물 및 음이온성 불순물을 포함한다. 그 밖의 성분으로서 물도 포함할 수 있다. 상기 금속 불순물로서는, 적어도 Ag, Al, Au, Ca, Cr, Cu, Fe, K, Mg, Na, Sn 및 Zn을 들 수 있다. 본 발명에 있어서의 미정제 카복실산 에스터에 있어서, 상기 금속 불순물의 함유량은 Ag, Al, Au, Ca, Cr, Cu, Fe, K, Mg, Na, Sn 및 Zn에 대해 각각 8ppb 이상인 것이 바람직하다. 또한, 상기 음이온 불순물의 함유량은 20ppm 이상인 것이 바람직하다. 본 발명에서는, 이와 같이 불순물 농도가 높은 미정제 카복실산 에스터를 이용했다고 하더라도, 고순도의 카복실산 에스터를 제조할 수 있다.The crude carboxylic acid ester in the present invention includes metal impurities and anionic impurities. Other components may also include water. Examples of the metal impurities include at least Ag, Al, Au, Ca, Cr, Cu, Fe, K, Mg, Na, Sn and Zn. In the crude carboxylic acid ester of the present invention, the content of the metal impurity is preferably 8 ppb or more with respect to each of Ag, Al, Au, Ca, Cr, Cu, Fe, K, Mg, Na, Sn and Zn. The content of the anion impurity is preferably 20 ppm or more. In the present invention, even if a crude carboxylic acid ester having such a high impurity concentration is used, a carboxylic acid ester of high purity can be produced.
본 발명에서 이용하는 양이온 교환 수지(II)로서는, H형의 강산성 양이온 교환 수지나 Na형의 강산성 양이온 교환 수지가 바람직하지만, 그 중에서도 설폰산기를 갖는 H형의 강산성 양이온 교환 수지가 특히 적합하게 사용될 수 있다. 상기 양이온 교환 수지는 시판 제품을 사용할 수도 있고, 구체적으로는 15JS-HG·DRY(오르가노사제)를 들 수 있다.As the cation exchange resin (II) used in the present invention, H strongly acidic cation exchange resins and Na strongly acidic cation exchange resins are preferable. Among them, H type strongly acidic cation exchange resins having sulfonic acid groups are particularly preferably used have. The cation exchange resin may be a commercially available product, specifically, 15JS-HG · DRY (manufactured by Organo).
본 발명에 있어서는, 후술하는 바와 같이, 1. 미정제 카복실산 에스터를 양이온 교환 수지에 접촉시킨 후에 음이온 교환 수지에 접촉시키는 방법, 2. 미정제 카복실산 에스터를 음이온 교환 수지에 접촉시킨 후에 양이온 교환 수지에 접촉시키고, 그 후 추가로 음이온 교환 수지에 접촉시키는 방법을 들 수 있다. 이하에 있어서, 양이온 교환 수지에 접촉시킨 후에 접촉시키는 음이온 교환 수지를 음이온 교환 수지(III), 또한 양이온 교환 수지에 접촉시키기 전에 접촉시키는 음이온 교환 수지를 음이온 교환 수지(I)로 표기하는 경우가 있다.In the present invention, as described later, 1. a method in which a crude carboxylic acid ester is contacted with a cation-exchange resin and then brought into contact with an anion-exchange resin, 2. a method in which a crude carboxylic acid ester is contacted with an anion- And then further contacting with an anion exchange resin. Hereinafter, an anion exchange resin to be brought into contact with the anion exchange resin after contact with the cation exchange resin is referred to as an anion exchange resin (III), and an anion exchange resin to be contacted with the anion exchange resin before contact with the cation exchange resin is referred to as anion exchange resin .
본 발명에서 이용하는 음이온 교환 수지(I) 및 (III)으로서는, 강염기성 음이온 교환 수지, 약염기성 음이온 교환 수지를 들 수 있지만, 약염기성 음이온 교환 수지가 바람직하고, 유리 염기형의 약염기성 음이온 교환 수지가 보다 바람직하다. 그 중에서도 제 3 암모늄 염기를 갖는 약염기성 음이온 교환 수지가 특히 적합하게 사용될 수 있다. 상기 음이온 교환 수지는 시판 제품을 사용할 수도 있고, 구체적으로는 B20-HG·DRY(오르가노사제)를 들 수 있다. 본 발명에 있어서, 음이온 교환 수지(I) 및 (III)은 동일 종류의 것이어도 되고 상이한 종류의 것이어도 된다.As the anion exchange resins (I) and (III) used in the present invention, a strong basic anion exchange resin and a weakly basic anion exchange resin can be mentioned, but a weakly basic anion exchange resin is preferable, and a free base anion exchange resin Is more preferable. Among them, a weakly basic anion exchange resin having a tertiary ammonium base can be suitably used. The anion exchange resin may be a commercially available product, and specifically may be B20-HG · DRY (manufactured by Organo). In the present invention, the anion exchange resins (I) and (III) may be of the same kind or of different kinds.
본 발명에 있어서의 미정제 카복실산 에스터를 양이온 교환 수지(II) 및 음이온 교환 수지(I), (III)에 접촉시키는 방법은 특별히 제한되지 않지만, 미정제 카복실산 에스터를 이들 양이온 교환 수지 및 음이온 교환 수지에 대해서 통액하는 방법이 일반적이다. 접촉시킬 때의 온도 조건으로서는, 이온 교환 수지의 내구성을 고려하면, 미정제 카복실산 에스터, 양이온 교환 수지 및 음이온 교환 수지의 온도를 100℃ 이하로 하는 것이 바람직하다. 또한, 본 발명의 제조법은 배치법, 유통법 어느 방법에 의해서도 행할 수 있지만, 정제 효율의 면에서 이온 교환 수지를 충전한 탑에 통액하는 유통법이 바람직하다. 유통법으로 정제하는 경우, 송액 방법은 상승류여도 하강류여도 되고, 통액의 공간 속도(SV: Hr-1)로서는, 액의 종류나 점도, 수지의 압력 손실 등에 따라 적절히 결정되지만, 바람직하게는 1∼50Hr-1, 더 바람직하게는 10∼20Hr-1이다. 미정제 카복실산 에스터 중의 수분 농도에 규정은 없지만, 수분을 포함하는 카복실산 에스터를 양이온 교환 수지에 접촉, 통액시킨 경우, 가수분해에 의해 산분(酸分)이 생긴다. 이 증가한 산분을 포함하는 카복실산 에스터를 다음에 음이온 교환 수지에 접촉, 통액시켰을 때, 생긴 산분이 음이온 교환 수지에 보족되어 음이온 교환 수지의 수명을 짧게 하기 때문에, 미정제 카복실산 에스터 중의 수분 농도는 0.01 중량% 이하인 것이 바람직하다.The method of bringing the crude carboxylic acid ester in the present invention into contact with the cation exchange resin (II) and the anion exchange resin (I) or (III) is not particularly limited, but the method of reacting the crude carboxylic acid ester with these cation exchange resins and anion exchange resins And the like. As the temperature condition at the time of contact, it is preferable to set the temperature of the crude carboxylic acid ester, the cation-exchange resin and the anion-exchange resin to 100 ° C or less in consideration of the durability of the ion-exchange resin. Further, the production method of the present invention can be carried out by any of the batch method and the distribution method, but from the viewpoint of purification efficiency, the circulation method is preferable in which the solution is passed through a column filled with an ion exchange resin. In the case of refining by the distribution method, the pumping method may be either ascending or descending, and the spatial velocity (SV: Hr- 1 ) of the passing liquid may be suitably determined according to the type and viscosity of the liquid, the pressure loss of the resin, 1 to 50 Hr -1 , more preferably 10 to 20 Hr -1 . The water concentration in the crude carboxylic acid ester is not specified, but when the carboxylic acid ester containing water is contacted with and passed through the cation exchange resin, the acid component is generated by hydrolysis. When the carboxylic acid ester containing the increased acid is then contacted with and passed through the anion exchange resin, the generated acid component stays in the anion exchange resin to shorten the lifetime of the anion exchange resin. Therefore, the water concentration in the crude carboxylic acid ester is 0.01 weight % Or less.
본 발명의 고순도 카복실산 에스터의 제조 방법으로서는, 양이온 교환 수지(II)에 접촉시키기 전에, 음이온 교환 수지(I)에 접촉시키는 방법이 보다 바람직하다. 미정제 카복실산 에스터를 양이온 교환 수지(II)에 접촉시키면, 전술한 바와 같이 미정제 카복실산 에스터 중에 포함되는 수분과 카복실산 에스터의 가수분해 반응에 의해, 새롭게 음이온성 불순물이 생성된다. 상기의 방법에 의하면, 양이온 교환 수지(II)에 접촉시키기 전에 미정제 카복실산 에스터 중에 포함되는 음이온성 불순물(당해 카복실산)을, 미리 음이온 교환 수지(I)에 접촉시켜 보족하는 것에 의해, 후에 음이온 교환 수지(III)가 보족하는 음이온성 불순물량의 부하가 경감되기 때문에, 음이온 교환 수지(III)의 수명을 개선할 수 있다.As a production method of the high purity carboxylic acid ester of the present invention, a method of bringing the anion exchange resin (I) into contact with the cation exchange resin (II) is more preferable. When the crude carboxylic acid ester is brought into contact with the cation exchange resin (II), anionic impurities are newly produced by the hydrolysis reaction between the water contained in the crude carboxylic acid ester and the carboxylic acid ester, as described above. According to the above method, the anionic impurities (carboxylic acid) contained in the crude carboxylic acid ester before contact with the cation exchange resin (II) are brought into contact with the anion exchange resin (I) in advance, The lifetime of the anion exchange resin (III) can be improved because the load of the amount of the anionic impurities which the resin (III) is insufficient is reduced.
실시예Example
이하, 본 발명을 구체적으로 설명하기 위해서 실시예 및 비교예를 들어 설명한다. 단, 본 발명은 이들 실시예로 한정되는 것은 아니다. 한편, 카복실산 에스터 중의 금속 불순물 농도 및 음이온성 불순물 농도의 분석은 이하에 나타내는 대로 행했다.EXAMPLES Hereinafter, the present invention will be described in detail with reference to examples and comparative examples. However, the present invention is not limited to these examples. On the other hand, the metal impurity concentration and the anionic impurity concentration in the carboxylic acid ester were analyzed as follows.
<금속 불순물 농도의 분석><Analysis of metal impurity concentration>
ICP 질량 분석계(Agilent사제, Agilent 7900 ICP-MS)에 의해 정량 분석했다.And quantitatively analyzed by an ICP mass spectrometer (Agilent 7900 ICP-MS, manufactured by Agilent).
<음이온성 불순물 농도의 분석>≪ Analysis of anionic impurity concentration >
0.01mol/L의 수산화 나트륨을 이용하여 자동 적정 장치(교토전자사제, 자동 적정 장치 AT-510)로 정량 분석했다. 분석은 50mL의 카복실산 에스터에 30mL의 메탄올을 가한 후에 행했다.And quantitatively analyzed with an automatic titration apparatus (automatic titrator AT-510 manufactured by Kyoto Electronics Co., Ltd.) using 0.01 mol / L sodium hydroxide. The analysis was carried out after adding 30 mL of methanol to 50 mL of the carboxylic acid ester.
<실시예 1>≪ Example 1 >
전처리로서 H형의 강산성 양이온 교환 수지(상품명: 오르가노사제 15JS-HG·DRY) 및 유리 염기형의 약염기성 음이온 교환 수지(상품명: 오르가노사제 B20-HG·DRY)를 락트산 에틸에 각각 따로따로 넣고, 적절히 완만하게 교반하면서 1시간 이상 침지했다. 그 후, 내경 16mm의 FEP제 컬럼 1개에 10ml의 강산성 양이온 교환 수지, 2개에 10ml씩 약염기성 음이온 교환 수지를 충전한 후, 락트산 에틸을 25℃에서 SV=20Hr-1로, 도 1에 나타내는 바와 같이, 약염기성 음이온 교환 수지(I), 강산성 양이온 교환 수지(II) 및 약염기성 음이온 교환 수지(III)의 순으로 통액했다. 통액 후의 각 불순물 농도를 표-1에 나타냈다. 표-1로부터 기재한 모든 금속, 및 음이온분이 고도로 제거되어 있음을 알 수 있다.As a pretreatment, a strongly acidic cation exchange resin (trade name: 15GS-HG DRY) of H type and a weak basic anion exchange resin of free base type (trade name: B20-HG, DRY, manufactured by Organo) were separately added to ethyl lactate And immersed for 1 hour or more while gently stirring. Thereafter, 10 ml of strongly acidic cation exchange resin and 10 ml of weakly basic anion exchange resin were charged into one column made of FEP having an inner diameter of 16 mm, and ethyl lactate was then added at 25 캜 to SV = 20 Hr -1 , (I), strongly acidic cation-exchange resin (II) and weakly basic anion-exchange resin (III) in this order, as shown in Fig. The concentration of each impurity after passing through is shown in Table-1. It can be seen that all of the metals and anions listed in Table 1 are highly removed.
<실시예 2>≪ Example 2 >
전처리로서 H형의 강산성 양이온 교환 수지(상품명: 오르가노사제 15JS-HG·DRY) 및 유리 염기형의 약염기성 음이온 교환 수지(상품명: 오르가노사제 B20-HG·DRY)를 하이드록시아이소뷰티르산 메틸에 각각 따로따로 넣고, 적절히 완만하게 교반하면서 1시간 이상 침지했다. 그 후, 내경 16mm의 FEP제 컬럼 1개에 10ml의 강산성 양이온 교환 수지, 2개에 10ml씩 약염기성 음이온 교환 수지를 충전한 후, 하이드록시아이소뷰티르산 메틸을 25℃에서 SV=20Hr-1로, 도 1에 나타내는 바와 같이, 약염기성 음이온 교환 수지(I), 강산성 양이온 교환 수지(II) 및 약염기성 음이온 교환 수지(III)의 순으로 통액했다. 통액 후의 각 불순물 농도를 표-2에 나타냈다. 표-2로부터 기재한 모든 금속, 및 음이온분이 고도로 제거되어 있음을 알 수 있다.As a pretreatment, a strongly acidic cation exchange resin (trade name: 15GS-HG · DRY) and a weak basic anion exchange resin (trade name: Organosan B20-HG · DRY) of H type were dissolved in methyl hydroxy isobutyrate Respectively, and immersed for 1 hour or more with gentle stirring as appropriate. Subsequently, 10 ml of strongly acidic cation exchange resin and two 10 ml of weakly basic anion exchange resin were charged to one column made of FEP having an inner diameter of 16 mm, and methyl hydroxy isobutyrate was then added at 25 ° C to SV = 20Hr -1 , The weakly basic anion exchange resin (I), the strongly acidic cation exchange resin (II) and the weakly basic anion exchange resin (III) were passed through in this order as shown in Fig. The concentration of each impurity after passing through is shown in Table 2. It can be seen that all of the metals and anions listed from Table 2 are highly removed.
추가로, 통액량을 늘려, 통액 후의 음이온성 불순물의 농도를 표-3에 나타냈다. 표-3으로부터, 음이온분에 관해서, 통액 개시로부터 2000ml까지는 고도로 제거되었지만, 2500ml 이후에서는 음이온분의 상승이 확인되었다.In addition, the amount of the liquid flow was increased, and the concentration of the anionic impurities after passing through was shown in Table-3. From Table 3, the anion content was highly removed from the initiation of permeation to 2000 ml, but the anion content was ascertained after 2500 ml.
<실시예 3>≪ Example 3 >
H형의 강산성 양이온 교환 수지(상품명: 오르가노사제 15JS-HG·DRY) 및 유리 염기형의 약염기성 음이온 교환 수지(상품명: 오르가노사제 B20-HG·DRY)를 실시예 2와 마찬가지로 하이드록시아이소뷰티르산 메틸로 전처리 후, 내경 16mm의 FEP제 컬럼 1개에 10ml의 강산성 양이온 교환 수지, 1개에 10ml의 약염기성 음이온 교환 수지를 충전한 후, 하이드록시아이소뷰티르산 메틸을 25℃에서 SV=20Hr-1로 강산성 양이온 교환 수지(II) 및 약염기성 음이온 교환 수지(III)의 순으로 통액했다. 통액 후의 각 불순물 농도를 표-4에 나타냈다. 표-4로부터 기재한 모든 금속이 고도로 제거되어 있음을 알 수 있다. 음이온분에 관해서는, 통액 개시로부터 1500ml까지는 고도로 제거되었지만, 1500ml 이후에서는 음이온분의 상승이 확인되었다.H-type strongly acidic cation exchange resin (trade name: 15GS-HG DRY manufactured by Organo Company) and a weak basic anion exchange resin (trade name: B20-HG, DRY manufactured by Organos Inc.) After pre-treatment with methyl butyrate, 10 ml of strongly acidic cation exchange resin and one 10 ml of weakly basic anion exchange resin were charged in one FEP column having an inner diameter of 16 mm, and methyl hydroxy isobutyrate was added at 25 ° C to SV = (II) and weakly basic anion exchange resin (III) in the order of 20Hr -1 . The concentration of each impurity after passing through is shown in Table 4. It can be seen that all of the metals listed in Table 4 are highly removed. With respect to the anion component, it was highly removed up to 1500 ml from the beginning of the passage, but the anion component increased after 1500 ml.
실시예 2 및 3의 결과로부터, 하이드록시아이소뷰티르산 메틸을 강산성 양이온 교환 수지(II)에 통액하기 전에, 약염기성 음이온 교환 수지(I)에 통액시킨 실시예 2 쪽이, 음이온 성분의 제거능이 개선되고, 게다가 음이온 교환 수지(III)의 수명을 개선할 수 있다.From the results of Examples 2 and 3, it can be seen from Example 2 that the methyl hydroxy isobutyrate was passed through the weakly basic anion exchange resin (I) before passing through the strongly acidic cation exchange resin (II) It is possible to improve the lifetime of the anion exchange resin (III).
<비교예 1>≪ Comparative Example 1 &
H형의 강산성 양이온 교환 수지(상품명: 오르가노사제 15JS-HG·DRY)를 실시예 1과 마찬가지로 락트산 에틸로 전처리 후, 내경 16mm의 FEP제 컬럼에 20ml 충전한 후, 락트산 에틸을 25℃에서 SV=20Hr-1로 통액했다. 통액 후의 각 불순물 농도를 표-5에 나타냈다. 표-5로부터 Ag, Au, Cr, Fe, Sn이 거의 제거되어 있지 않고, 또한 음이온성 불순물이 제거되어 있지 않음을 알 수 있다.As in Example 1, H-type strongly acidic cation exchange resin (trade name: 15JS-HG DRY) was pretreated with ethyl lactate, and after filling the column with 20 ml of FEP column having an inner diameter of 16 mm, = 20Hr < -1 & gt ;. The concentration of each impurity after passing through was shown in Table 5. It can be seen from Table 5 that almost no Ag, Au, Cr, Fe and Sn were removed and an anionic impurity was not removed.
<비교예 2>≪ Comparative Example 2 &
유리 염기형의 약염기성 음이온 교환 수지(상품명: 오르가노사제 B20-HG·DRY)를 실시예 1과 마찬가지로 락트산 에틸로 전처리 후, 내경 16mm의 FEP제 컬럼에 20ml 충전한 후, 락트산 에틸을 25℃에서 SV=20Hr-1로 통액했다. 통액 후의 각 불순물 농도를 표-6에 나타냈다. 표-6으로부터 K, Na가 거의 제거되어 있지 않음을 알 수 있다.The free basic anion exchange resin (trade name: B20-HG DRY manufactured by Organo Corp.) was pretreated with ethyl lactate in the same manner as in Example 1, and then filled in a column made of FEP having an inner diameter of 16 mm in an amount of 20 ml. To SV = 20Hr < -1 & gt ;. The concentration of each impurity after passing through is shown in Table 6. From Table 6, it can be seen that K and Na are hardly removed.
<비교예 3>≪ Comparative Example 3 &
H형의 강산성 양이온 교환 수지(상품명: 오르가노사제 15JS-HG·DRY) 10ml와 유리 염기형의 약염기성 음이온 교환 수지(상품명: 오르가노사제 B20-HG·DRY) 20ml를 혼합하고 락트산 에틸로 실시예 1과 마찬가지의 전처리 후, 내경 16mm의 FEP제 컬럼에 30ml 충전한 후, 락트산 에틸을 25℃에서 SV=20Hr-1로 통액했다. 통액 후의 각 불순물 농도를 표-7에 나타냈다. 표-7로부터 Ca, Cr의 제거가 불충분함을 알 수 있다.10 ml of strongly acidic cation exchange resin (trade name: 15GS-HG · DRY) and 20 ml of weak basic anion exchange resin (trade name: Organosan B20-HG · DRY) were mixed with ethyl lactate After the pretreatment in the same manner as in Example 1, 30 ml of an FEP column having an inner diameter of 16 mm was filled, and then ethyl lactate was passed at 25 캜 at SV = 20 Hr -1 . The concentration of each impurity after passing through is shown in Table 7. From Table 7, it can be seen that the removal of Ca and Cr is insufficient.
<비교예 4>≪ Comparative Example 4 &
H형의 강산성 양이온 교환 수지(상품명: 오르가노사제 15JS-HG·DRY)를 실시예 2와 마찬가지로 하이드록시아이소뷰티르산 메틸로 전처리 후, 내경 16mm의 FEP제 컬럼에 20ml 충전한 후, 하이드록시아이소뷰티르산 메틸을 25℃에서 SV=20Hr-1로 통액했다. 통액 후의 각 불순물 농도를 표-8에 나타냈다. 표-8로부터 Ag, Au, Fe, Sn이 거의 제거되어 있지 않고, 또한 음이온성 불순물이 제거되어 있지 않음을 알 수 있다.The strongly acidic cation exchange resin of the H type (trade name: 15JS-HG DRY) was pre-treated with methyl hydroxy isobutyrate in the same manner as in Example 2, and then filled in a column made of FEP having an inner diameter of 16 mm in an amount of 20 ml. Methyl butyrate was passed at 25 DEG C at SV = 20Hr < -1 >. The concentration of each impurity after passing through is shown in Table 8. It can be seen from Table 8 that Ag, Au, Fe, and Sn were hardly removed, and anionic impurities were not removed.
<비교예 5>≪ Comparative Example 5 &
유리 염기형의 약염기성 음이온 교환 수지(상품명: 오르가노사제 B20-HG·DRY)를 실시예 2와 마찬가지로 하이드록시아이소뷰티르산 메틸로 전처리 후, 내경 16mm의 FEP제 컬럼에 20ml 충전한 후, 하이드록시아이소뷰티르산 메틸을 25℃에서 SV=20Hr-1로 통액했다. 통액 후의 각 불순물 농도를 표-9에 나타냈다. 표-9로부터 K, Na가 거의 제거되어 있지 않음을 알 수 있다.The free basic anion exchange resin (trade name: B20-HG, DRY manufactured by Organos Inc.) was pretreated with methyl hydroxy isobutyrate in the same manner as in Example 2, and then filled in a column made of FEP having an inner diameter of 16 mm in an amount of 20 ml. Methyloxyisobutyrate was passed at 25 DEG C at SV = 20Hr < -1 >. The concentration of each impurity after passing through is shown in Table-9. From Table 9, it can be seen that K and Na are hardly removed.
<비교예 6>≪ Comparative Example 6 >
H형의 강산성 양이온 교환 수지(상품명: 오르가노사제 15JS-HG·DRY) 10ml와 유리 염기형의 약염기성 음이온 교환 수지(상품명: 오르가노사제 B20-HG·DRY) 20ml를 혼합하고 하이드록시아이소뷰티르산 메틸로 실시예 2와 마찬가지의 전처리 후, 내경 16mm의 FEP제 컬럼에 30ml 충전한 후, 하이드록시아이소뷰티르산 메틸을 25℃에서 SV=20Hr-1로 통액했다. 통액 후의 각 불순물 농도를 표-10에 나타냈다. 표-10으로부터 Ca, Cr의 제거가 불충분함을 알 수 있다.10 ml of a strongly acidic cation exchange resin (trade name: 15GS-HG · DRY) of H type and 20 ml of a weak base anion exchange resin of free base type (trade name: B20-HG · DRY manufactured by Organo) were mixed, After pretreating in the same manner as in Example 2, 30 ml of an FEP column having an inner diameter of 16 mm was filled with 30 ml of methyl hydroxy isobutyrate at a temperature of 25 ° C at a temperature of SV = 20 Hr -1 . The concentration of each impurity after passing through is shown in Table 10. From Table 10, it can be seen that the removal of Ca and Cr is insufficient.
본 발명에서 제공되는 고순도 카복실산 에스터는 고도로 금속 불순물 및 음이온성 불순물이 저감되어 있어, 산업상 유용하다. 카복실산 에스터는 합성 원료, 전자 부품의 세정제나 도료, 접착제 등의 용제 등의 폭넓은 용도로서, 또한 집적 회로나 대규모 집적 회로의 제조에 있어서의 반도체 기판의 세정, 식각, 포토레지스트의 현상 등을 위한 처리제로서 유용한 화합물이다.The high-purity carboxylic acid ester provided in the present invention is industrially useful because the metal impurities and the anionic impurities are highly reduced. The carboxylic acid ester can be used for a wide range of applications such as synthesis materials, cleaning agents for electronic components, solvents such as paints and adhesives, and for cleaning semiconductor substrates, etching, and photoresist development in the manufacture of integrated circuits and large-scale integrated circuits It is a compound useful as a treating agent.
Claims (6)
상기 양이온 교환 수지(II)에 접촉시키기 전에, 음이온 교환 수지(I)에 접촉시키는 공정을 포함하는, 고순도 카복실산 에스터의 제조 방법.3. The method of claim 2,
(I), before contacting the cation exchange resin (II) with the anion exchange resin (I).
상기 카복실산 에스터가 락트산 메틸, 락트산 에틸, 락트산 프로필, α-하이드록시아이소뷰티르산 메틸, α-하이드록시아이소뷰티르산 에틸, α-하이드록시아이소뷰티르산 프로필, α-하이드록시아이소뷰티르산 뷰틸, β-하이드록시아이소뷰티르산 메틸, β-하이드록시아이소뷰티르산 에틸, β-하이드록시아이소뷰티르산 프로필 및 β-하이드록시아이소뷰티르산 뷰틸로 이루어지는 군으로부터 선택되는 적어도 1종인, 고순도 카복실산 에스터의 제조 방법.The method according to claim 2 or 3,
Wherein the carboxylic acid ester is selected from the group consisting of methyl lactate, ethyl lactate, propyl lactate, methyl? -Hydroxyisobutyrate,? -Hydroxy isobutyrate,? -Hydroxyisobutyrate,? -Hydroxyisobutyrate, A method for producing a high purity carboxylic acid ester which is at least one selected from the group consisting of methyl hydroxyisobutyrate, methyl β-hydroxyisobutyrate, propyl β-hydroxyisobutyrate, and β-hydroxyisobutyrate butyl .
얻어진 고순도 카복실산 에스터에 있어서, 상기 금속 불순물의 함유율이 Ag, Al, Au, Ca, Cr, Cu, Fe, K, Mg, Na, Sn 및 Zn에 대해 각각 1ppb 미만이고, 상기 음이온성 불순물의 함유율이 1ppm 미만인, 고순도 카복실산 에스터의 제조 방법.5. The method according to any one of claims 2 to 4,
The obtained high purity carboxylic acid ester had a content of the metal impurity of less than 1 ppb for each of Ag, Al, Au, Ca, Cr, Cu, Fe, K, Mg, Na, Sn and Zn, ≪ / RTI > less than 1 ppm.
상기 미정제 카복실산 에스터에 있어서, 상기 금속 불순물의 함유율이 Ag, Al, Au, Ca, Cr, Cu, Fe, K, Mg, Na, Sn 및 Zn에 대해 각각 8ppb 이상이고, 상기 음이온 불순물의 함유량이 20ppm 이상인, 고순도 카복실산 에스터의 제조 방법.6. The method according to any one of claims 2 to 5,
Wherein the content of the metal impurity in the crude carboxylic acid ester is 8 ppb or more with respect to each of Ag, Al, Au, Ca, Cr, Cu, Fe, K, Mg, Na, Sn and Zn, 20 ppm or higher.
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| CN107389834B (en) * | 2017-07-12 | 2022-11-01 | 中国地质大学（武汉） | Visual low pressure isotope separation chromatographic column |
| JP7229023B2 (en) * | 2019-01-24 | 2023-02-27 | 倉敷繊維加工株式会社 | Method for Filtration of Chemical Solution Containing Carboxylic Acid Derivative |
| WO2023169810A1 (en) | 2022-03-11 | 2023-09-14 | Röhm Gmbh | Process for producing alpha-hydroxyisobutyric acid methyl ester, and its use in the electronics industry |
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